CN107768674B - Electrolytic copper foil, electrode, secondary battery, and method for producing electrolytic copper foil - Google Patents

Electrolytic copper foil, electrode, secondary battery, and method for producing electrolytic copper foil Download PDF

Info

Publication number
CN107768674B
CN107768674B CN201710729000.9A CN201710729000A CN107768674B CN 107768674 B CN107768674 B CN 107768674B CN 201710729000 A CN201710729000 A CN 201710729000A CN 107768674 B CN107768674 B CN 107768674B
Authority
CN
China
Prior art keywords
copper foil
electrolytic copper
active material
layer
protective layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710729000.9A
Other languages
Chinese (zh)
Other versions
CN107768674A (en
Inventor
金星玟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KCF Technologies Co Ltd
Original Assignee
KCF Technologies Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020160107230A external-priority patent/KR102669501B1/en
Application filed by KCF Technologies Co Ltd filed Critical KCF Technologies Co Ltd
Publication of CN107768674A publication Critical patent/CN107768674A/en
Application granted granted Critical
Publication of CN107768674B publication Critical patent/CN107768674B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/06—Filtering particles other than ions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/04—Electroplating with moving electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12431—Foil or filament smaller than 6 mils
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12431—Foil or filament smaller than 6 mils
    • Y10T428/12438—Composite

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Provided are an electrolytic copper foil capable of ensuring a high capacity retention rate of a secondary battery, an electrode including an electrolytic copper foil capable of ensuring a high capacity retention rate of a secondary battery, a secondary battery including an electrolytic copper foil capable of ensuring a high capacity retention rate of a secondary battery, and a method for producing an electrolytic copper foil capable of ensuring a high capacity retention rate of a secondary battery. The electrolytic copper foil includes a first surface, and a second surface opposite to the first surface, a copper layer including a matte side facing the first surface and a glossy side facing the second surface, and a first protective layer; the first protective layer is disposed on the matte side of the copper layer, wherein the first protective layer includes chromium (Cr), and an adhesion coefficient of the first surface of the electrolytic copper foil ranges from 1.5 to 16.3.

Description

Electrolytic copper foil, electrode, secondary battery, and method for producing electrolytic copper foil
The present application claims priority and benefit from korean patent application No. 10-2016-0107230, filed on 8/23/2016, the disclosure of which is incorporated herein by reference in its entirety.
Technical Field
The present invention relates to an electrolytic copper foil, an electrode including the electrolytic copper foil, a secondary battery including the electrolytic copper foil, and a method of manufacturing the electrolytic copper foil.
Background
A secondary battery is an energy conversion device for converting electric energy into chemical energy, storing the chemical energy, and generating electric power by converting the chemical energy into electric energy when electric power is required, and is therefore also called a "rechargeable battery".
Lead-acid batteries, cadmium secondary batteries, nickel metal hydride secondary batteries, lithium batteries, and the like are economically and environmentally superior to primary batteries.
Lithium batteries can store a significant amount of electricity relative to the size and weight of other batteries. Portability and flowability are important factors in the field of information communication equipment, and therefore, a lithium battery is a preferable choice, and its application range is also expanded to an energy storage device for hybrid vehicles and electric vehicles.
The lithium battery is used by repeating cycles of charge and discharge. When operating a device carrying a fully charged lithium battery, the lithium battery should have a sufficiently high charge-discharge capacity to increase the operating time of the device. Therefore, there is a continuing need to meet consumer expectations for increased charge and discharge capacity of lithium batteries.
Meanwhile, even if the charge and discharge capacity of the secondary battery is sufficiently large, the charge and discharge capacity of the secondary battery is rapidly reduced due to repeated charge and discharge cycles, for example, the capacity retention rate (capacity retention rate) of the secondary battery is low or the life of the secondary battery is short, and the consumer needs to frequently renew the secondary battery, thereby causing inconvenience and resource waste.
Disclosure of Invention
The present invention is directed to providing an electrolytic copper foil that can avoid the problems due to the limitations and disadvantages of the related art, an electrode including an electrolytic copper foil that can avoid the problems due to the limitations and disadvantages of the related art, a secondary battery including an electrolytic copper foil that can avoid the problems due to the limitations and disadvantages of the related art, and a method of manufacturing an electrolytic copper foil that includes a electrolytic copper foil that can avoid the problems due to the limitations and disadvantages of the related art.
The present invention relates to an electrolytic copper foil which can ensure a high capacity retention rate of a secondary battery.
The invention relates to an electrode which ensures a high capacity retention of a battery.
The present invention relates to a secondary battery having a high capacity retention rate.
The present invention relates to a method for producing an electrolytic copper foil capable of securing a high capacity retention rate of a secondary battery.
In addition to the above aspects of the invention, other features and advantages of the invention are described below; or that certain undescribed features and advantages of the invention will be apparent to those skilled in the art from the following description.
An aspect of the present invention is to provide an electrolytic copper foil including a first surface, and a second surface opposite to the first surface, a copper layer including a matte side facing the first surface and a glossy side facing the second surface, and a first protective layer; a first protective layer disposed on the matte side of the copper layer, wherein the first protective layer comprises chromium (Cr); wherein the adhesion coefficient of the surface is defined by the following equation 1:
equation 1: ADF Pc/10+ DACr/(mg/m2)+Rmax/μm；
Here, ADF denotes the adhesion coefficient, Pc denotes a peak count (peak count), DACrRepresents the plating amount (mg/m) of chromium (Cr)2) And RmaxThe maximum surface roughness (μm) is shown.
In addition, the adhesion coefficient of the first surface ranges from 1.5 to 16.3, the peak count (Pc) of the first surface ranges from 5 to 110, and the plating amount (DA) of chromium of the first surfaceCr) Ranging from 0.5mg/m2To 3.8mg/m2And the maximum surface roughness (R) of the first surfacemax) Ranging from 0.4 μm to 3.5 μm.
The electrolytic copper foil also comprises a second protective layer arranged on the glossy surface of the copper layer; wherein the second protective layer comprises chromium (Cr), and the second surface has an adhesion coefficient in a range of 1.5 to 16.3.
The peak count (Pc) of the second surface ranges from 5 to 110, the plating amount (DA) of chromium of the second surfaceCr) Ranging from 0.5mg/m2To 3.8mg/m2And the maximum surface roughness (R) of the second surfacemax) Ranging from 0.4 μm to 3.5 μm.
The yield strength of the electrolytic copper foil at room temperature was 21kgf/mm2To 63kgf/mm2。
The electrolytic copper foil has an elongation of 3% or more at room temperature.
Another aspect of the present invention is to provide a battery electrode comprising an electrolytic copper foil comprising a first surface, and a second surface opposite the first surface; and a first active material layer disposed on a first surface of the electrolytic copper foil, wherein the electrolytic copper foil includes a copper layer including a matte surface facing the first surface and a glossy surface facing the second surface, and a first protective layer disposed on the matte surface of the copper layer, and the first protective layer includes chromium (Cr); wherein the adhesion coefficient of the surface is defined by the following equation 1:
equation 1: ADF Pc/10+ DACr/(mg/m2)+Rmax/μm；
Here, ADF denotes the adhesion coefficient, Pc denotes the peak count, DACrRepresents the plating amount (mg/m) of chromium (Cr)2)，RmaxRepresents the maximum surface roughness (μm); wherein the first surface has an adhesion coefficient ranging from 1.5 to 16.3.
The first active material layer includes at least one active material selected from the group consisting of carbon, a metal, an alloy including the foregoing metal, an oxide of the foregoing metal, and a composite of the foregoing metal and carbon, wherein the foregoing metal is silicon, germanium, tin, lithium, zinc, magnesium, cadmium, cerium, nickel, or iron.
The first active material layer includes silicon.
The electrolytic copper foil also comprises a second protective layer arranged on the glossy surface of the copper layer; the battery electrode also includes a second active material layer disposed on the second protective layer.
The adhesion between the electrolytic copper foil and the first active material layer is 25N/m or more.
It is another aspect of the present invention to provide a battery including a cathode, an anode including a battery electrode, an electrolyte configured to provide an environment in which lithium ions can move between the cathode and the anode, and a separator configured to electrically insulate the anode from the cathode. The anode comprises an electrolytic copper foil, and the electrolytic copper foil comprises a first surface and a second surface opposite to the first surface; and a first active material layer disposed on a first surface of the electrolytic copper foil, wherein the electrolytic copper foil includes a copper layer including a matte surface facing the first surface and a glossy surface facing the second surface, and a first protective layer disposed on the matte surface of the copper layer, wherein the first protective layer includes chromium (Cr); wherein the adhesion coefficient of the surface is defined by the following equation 1:
equation 1: ADF Pc/10+ DACr/(mg/m2)+Rmax/μm；
Here, ADF denotes an adhesion coefficient, Pc denotes a peak count (peak count), DACrRepresents the plating amount (mg/m) of chromium (Cr)2) And RmaxRepresents the maximum surface roughness (μm); wherein the first surface has an adhesion coefficient ranging from 1.5 to 16.3.
The first active material layer includes at least one active material selected from the group consisting of carbon, a metal, an alloy including the foregoing metal, an oxide of the foregoing metal, and a composite of the foregoing metal and carbon, wherein the foregoing metal is silicon, germanium, tin, lithium, zinc, magnesium, cadmium, cerium, nickel, or iron.
The first active material layer includes silicon.
The electrolytic copper foil also comprises a second protective layer arranged on the glossy surface of the copper layer; the battery electrode also includes a second active material layer disposed on the second protective layer.
Another aspect of the present invention is to provide a method of manufacturing an electrolytic copper foil for a secondary battery, the method including forming a copper layer formed by supplying electricity between a positive electrode plate and a negative electrode rotating drum spaced apart from each other, the positive electrode plate and the negative electrode rotating drum being disposed in an electrolyte containing 70g/L to 90g/L of copper ions and 50g/L to 150g/L of sulfuric acid; and forming a protective layer on the copper layer, wherein the step of forming the copper layer includes heat-treating the copper wire; pickling the overheated copper wire; preparing an electrolyte by putting the acid-washed copper wire into sulfuric acid; by providing a current density of 40A/dm between the positive and negative rotating drums2To 80A/dm2Electroplating is carried out by the current; and at the time of plating, at 31m3Hour to 45m3Continuously filtering at a flow rate of one hour to remove solid impurities from the electrolyte, wherein a total carbon amount (TC) in the electrolyte is maintained at 0.25g/L or less, a silver (Ag) concentration in the electrolyte is maintained at 0.2g/L or less, and the formation of the protective layer may include immersing the copper layer in a rust preventive solutionThe rust preventive solution contains 0.5g/L to 1.5g/L of chromium.
The copper wire may be heat-treated at a temperature ranging from 600 ℃ to 900 ℃ for a time ranging from 30 minutes to 60 minutes.
The electrolyte may further include chloride ions that can react with silver (Ag) to form silver chloride (AgCl) precipitates, so as to prevent the concentration of silver (Ag) in the electrolyte from exceeding 0.2g/L due to the addition of silver when performing electroplating.
The forming of the copper layer further includes adding hydrogen peroxide and air to the electrolyte while performing the electroplating.
The copper (Cu) concentration in the rust inhibitive solution is maintained at 0.1g/L or less.
The electrolyte may further include an organic additive selected from the group consisting of hydroxyethyl cellulose (HEC), organic sulfides, organic nitrides, and thiourea-based compounds.
The general description of the invention as set forth above is intended only to illustrate or explain the invention and is not intended to limit the scope of the invention.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent to those of ordinary skill in the art by describing exemplary embodiments thereof with reference to the accompanying drawings, in which:
fig. 1 is a cross-sectional view of a battery electrode according to an embodiment of the present invention.
Fig. 2 shows a surface roughness profile obtained according to us standard ASME B46.1-2009.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Various modifications and alterations of this invention may be made without departing from the spirit and scope of this invention, as those skilled in the art will readily appreciate. Accordingly, this invention includes all modifications and alterations coming within the scope of the invention as defined by the appended claims and equivalents thereof.
A battery includes a cathode, an anode, an electrolyte configured to provide an environment in which lithium ions can move between the cathode and the anode, and a separator configured to electrically insulate the anode from the cathode, thereby preventing electrons generated from an inefficiently consumed electrode from moving through the interior of the battery to another electrode.
Fig. 1 is a cross-sectional view of a battery electrode according to an embodiment of the present invention.
As shown in fig. 1, the battery electrode 100 according to the embodiment of the present invention includes an electrolytic copper foil 110, and the electrolytic copper foil 110 includes a first surface S1, a second surface S2 opposite to the first surface S1, a first active material layer 120a disposed on the first surface S1, and a second active material layer 120b disposed on the second surface S2. In the embodiment of fig. 1, the active material layer 120a and the active material layer 120b are formed on the first surface S1 and the second surface S2 of the electrolytic copper foil 110, respectively, although the present invention is not limited thereto. In some embodiments, the battery electrode 100 of the present invention may include only one of the first and second active material layers 120a and 120b as an active material layer.
Generally, in a lithium battery, aluminum foil is used as a positive electrode current collector, and the positive electrode current collector is connected to a positive electrode active material. The electrolytic copper foil is used as a negative electrode current collector, and the negative electrode current collector is connected to a negative electrode active material.
According to an embodiment of the present invention, the battery electrode 100 is used as an anode of a lithium battery, the electrolytic copper foil 110 is used as a negative current collector, and the first active material layer 120a and the second active material layer 120b each include a negative active material.
As shown in fig. 1, the electrolytic copper foil 110 according to an embodiment of the present invention functions as a negative electrode current collector of a secondary battery, and the electrolytic copper foil 110 includes a copper layer 111, a first protective layer 112a, and a second protective layer 112b, the copper layer 111 includes a matte side MS and a glossy side SS, the first protective layer 112a is disposed on the matte side MS of the copper layer 111, and the second protective layer 112b is disposed on the glossy side SS of the copper layer 111.
The matte side MS is a surface of the copper layer 111 facing the first surface S1 of the electrolytic copper foil 110, and the glossy side SS is a surface of the copper layer 111 facing the second surface S2 of the electrolytic copper foil 110.
The copper layer 111 of the present invention can be formed on a negative electrode rotating drum (cathode) by electroplating. In some embodiments, the glossy surface SS refers to a surface that is in contact with the negative electrode rotary drum during the plating process, and the matte surface MS refers to a surface opposite to the glossy surface SS.
Generally, the glossy surface SS has a lower surface roughness (Rz) than the matte surface MS, but the present invention is not limited thereto. And the surface roughness (Rz) of the glossy surface SS may be greater than or equal to the surface roughness (Rz) of the matte surface MS. Here, the roughness of each of the glossy surface SS and the matte surface MS refers to ten-point average roughness (Rz).
The first protective layer 112a and the second protective layer 112b for preventing corrosion of the copper layer 111 and improving heat resistance of the copper layer 111 may be formed, and thus the first protective layer 112a and the second protective layer 112b may each include chromium (Cr), and a decrease in charge and discharge efficiency of the secondary battery may be suppressed by increasing adhesion strength between the copper layer 111 and the first active material layer 120a and the second active material layer 120 b.
In the embodiment of fig. 1, the first protective layer 112a and the second protective layer 112b are formed on the matte side MS of the copper layer 111 and the glossy side SS of the copper layer 111, respectively, as described above, but the present invention is not limited thereto. In some embodiments, the electrolytic copper foil 110 may include only one of the first protective layer 112a and the second protective layer 112b as a protective layer.
The electrolytic copper foil 110 of the secondary battery of the present invention may have a yield strength (yield strength) of 21kgf/mm at room temperature (25 ℃. + -. 15 ℃)2To 63kgf/mm2. The yield strength was measured by a Universal Test Machine (UTM) in which the width of the sample was 12.7mm, the distance between the clamps was 50mm, and the measurement speed was 50 mm/min. When the yield strength of the electrolytic copper foil 110 is less than 21kgf/mm2In time, the electrolytic copper foil 110 has a risk of wrinkling due to the force applied during the process of manufacturing the electrode 100 and the secondary battery. On the other hand, when the yield strength of the electrolytic copper foil 110 is more than 63kgf/mm2When the battery is manufactured, workability in the manufacturing process of the battery is reduced.
The electrolytic copper foil 110 of the secondary battery of the present invention has an elongation (elongation) of 3% or more at room temperature (25 ℃. + -. 15 ℃). When the elongation of the electrolytic copper foil 110 is less than 3%, the force applied during the process of manufacturing the electrode 100 and the secondary battery may not stretch the electrolytic copper foil 110, increasing the risk of tearing the electrolytic copper foil 110.
The electrolytic copper foil 110 of the present invention may have a thickness of 3 μm to 20 μm.
The first active material layer 120a and the second active material layer 120b each include at least one active material, and the active material as the negative electrode active material is selected from the group consisting of carbon, a metal, an alloy including the foregoing metal, an oxide of the foregoing metal, and a composite of the foregoing metal and carbon, wherein the foregoing metal is silicon, germanium, tin, lithium, zinc, magnesium, cadmium, cerium, nickel, or iron.
In order to increase the charge and discharge capacity of the secondary battery, the first active material layer 120a and the second active material layer 120b may be composed of a mixture including a predetermined amount of silicon.
Meanwhile, when the battery is repeatedly charged and discharged, the contraction and expansion of the first and second active material layers 120a and 120b alternately occur. The alternately occurring contraction and expansion causes the first active material layer 120a and the second active material layer 120b to be separated from the electrolytic copper foil 110, respectively, thereby causing a decrease in charge and discharge efficiency of the secondary battery. Therefore, in order to provide a sufficient capacity retention rate and a service life of the secondary battery of a certain degree or more (i.e., to suppress deterioration of the charge-discharge efficiency of the secondary battery), the electrolytic copper foil 110 should have excellent coverage for the active material so that the electrolytic copper foil 110 can have high adhesion strength with the first active material layer 120a and the second active material layer 120b, respectively.
In general, it is known that the adhesion strength between the electrolytic copper foil 110 and the first and second active material layers 120a and 120b, respectively, can be improved by controlling the surface roughness (Rz) of the electrolytic copper foil 110. However, in fact, the electrolytic copper foil 110 in which the ten-point average roughness (Rz) can be appropriately adjusted (for example, the surface roughness is adjusted to be less than or equal to 2 μm) does not necessarily satisfy the adhesion strength between the electrolytic copper foil 110 and the first active material layer 120a and the second active material layer 120b, respectively, which is required in the industry specifications. Therefore, the requirement that the capacity retention rate of the secondary battery required in the industry must be equal to or greater than 90% after 500 charges and discharges may not be guaranteed to be achieved.
Specifically, it is known that when the first active material layer 120a and the second active material layer 120b each include silicon that can increase the capacity of the secondary battery, the correlation between the ten-point average roughness (Rz) of the electrolytic copper foil 110 and the capacity retention rate of the secondary battery is low.
According to the present invention, the inventors found that sufficient adhesion between the electrolytic copper foil 110 and the first and second active material layers 120a and 120b, respectively, is secured so that the capacity retention rate of the secondary battery is greater than or equal to 90%. Important factors of the surface of the electrolytic copper foil 110 are (i) the peak count (Pc) and (ii) the plating amount (DA) of chromium (Cr)Cr)(mg/m2) And (iii) maximum surface roughness (R)max)(μm)。
And maximum surface roughness (R)max) Also, the peak count (Pc) affects the force of the physical bond between the electrolytic copper foil 110 and the first active material layer 120 a. The peak count (Pc) will be described below with reference to fig. 2.
In the present invention, the peak count (Pc) may be obtained by measuring peak counts at any three points on the first surface S1 of the electrolytic copper foil 110, and calculating an average of the measured peak count values as the peak count (Pc). In the surface roughness profile obtained according to U.S. standard ASME B46.1-2009, the effective peak rises above the upper standard line C1(0.5 μm) per unit sample length of 4mm, and the peak count (Pc) at each point is the number of effective peaks P1, P2, P3, and P4. In this case, between adjacent effective peaks between the effective peaks, there is at least one peak valley lower than the lower standard line C2(-0.5 μm). When there is no peak valley below the lower criterion line C2 between adjacent peaks rising above the upper criterion line C1, all of these adjacent peaks may not be "valid peaks" for measuring peak counts, and relatively lower peaks between valid peaks are ignored when obtaining the number of "valid peaks".
According to the present invention, one peak count (Pc) of the first surface S1 of the electrolytic copper foil 110 ranges from 5 to 110.
When the peak count (Pc) is less than 5, the active specific surface area of the electrolytic copper foil 110 may be too small to contact the negative active material, and sufficient adhesion between the electrolytic copper foil 110 and the first active material layer 120a may not be ensured. On the other hand, when the peak count (Pc) is greater than 110, the coating uniformity of the anode active material is reduced due to too many surface irregularities, and thus the adhesion between the electrolytic copper foil 110 and the first active material layer 120a is significantly reduced.
Plating amount of chromium (DA)Cr) Is a factor affecting the force of chemical bonds existing between the electrolytic copper foil 110 and the first active material layer 120a, and the plating amount of chromium (DA)Cr) Is measured by analyzing a solution obtained by dissolving the first surface S1 of the electrolytic copper foil 110 in dilute nitric acid (30 wt%) using Atomic Absorption Spectrometry (AAS).
According to the embodiment of the present invention, the plating amount (DA) of chromium of the first surface S1 of the electrolytic copper foil 110Cr) In the range of from 0.5mg/m2To 3.8mg/m2。
When plating amount of chromium (DA)Cr) Less than 0.5mg/m2In this case, the first surface S1 of the electrolytic copper foil 110 may be oxidized, and thus, it may not be possible to ensure sufficient adhesion between the electrolytic copper foil 110 and the first active material layer 120 a. On the other hand, when the plating amount of chromium (DA) is setCr) Greater than 3.8mg/m2When, the hydrophobicity of the first surface S1 of the electrolytic copper foil 110 is increased and the chemical affinity of the negative active material is decreased, so that the adhesion between the electrolytic copper foil 110 and the first active material layer 120a is significantly decreased.
Maximum surface roughness (R) as well as peak count (Pc)max) Is a factor affecting the force of physical bond between the electrolytic copper foil 110 and the first active material layer 120a, and the maximum surface roughness (R) is measured according to Japanese Industrial Standard (JIS) B0601-max) (measurement length: 4 mm).
According to the embodiment of the present invention, the maximum surface roughness (R) of the first surface S1 of the electrolytic copper foil 110max) In the range of from 0.4 μm to 3.5. mu.m.
When it is maximumSurface roughness (R)max) Less than 0.4 μm, the active specific surface area of the electrolytic copper foil 110 in contact with the negative electrode active material may be too small to ensure sufficient adhesion between the electrolytic copper foil 110 and the first active material layer 120 a. On the other hand, when the maximum surface roughness (R)max) Above 3.5 μm, the coating uniformity of the negative active material is reduced because the first surface S1 of the electrolytic copper foil 110 is too uneven, and thus the adhesion between the electrolytic copper foil 110 and the first active material layer 120a is significantly reduced.
According to the present invention, since the above-mentioned three factors complicatedly affect the adhesion between the electrolytic copper foil 110 and the first and second active material layers 120a and 120b, respectively, the adhesion coefficient (ADF) of the first surface S1 of the electrolytic copper foil 110 is controlled within the range of 1.5 to 16.3. The ADF is defined by the following equation 1:
equation 1: ADF Pc/10+ DACr/(mg/m2)+Rmax/μm；
Here, ADF denotes an adhesion coefficient, Pc denotes a peak count (number of effective peaks), DACrRepresents the plating amount (mg/m) of chromium (Cr)2)，RmaxThe maximum surface roughness (μm) is indicated.
When the value of the adhesion coefficient (ADF) is less than 1.5, the active specific surface area of the first surface S1 of the electrolytic copper foil 110 that can contact the negative electrode active material is too small, and thus the adhesion between the electrolytic copper foil 110 and the first active material layer 120a is lowered. On the other hand, when the value of the adhesion coefficient (ADF) is greater than 16.3, the affinity between the active material and the electrolytic copper foil 110 is reduced, the coating uniformity of the negative electrode active material is reduced due to too many surface irregularities, and therefore, the adhesion between the electrolytic copper foil 110 and the first active material layer 120a is significantly reduced.
The adhesion between the electrolytic copper foil 110 and the first active material layer 120a is, for example, 25N/m or more. The adhesion may be obtained from the peel strength between the electrolytic copper foil 110 and the first active material layer 120 a. More specifically, the adhesion between the electrolytic copper foil 110 and the first active material layer 120a ranges from 25N/m to 50N/m.
In the embodiment of the present invention shown in fig. 1, since both the first surface S1 and the second surface S2 of the electrolytic copper foil 110 are coated with the negative active material, both the first surface S1 and the second surface S2 of the electrolytic copper foil 110 have an adhesion coefficient (ADF) having a value of 1.5 to 16.3.
Further, the peak count (Pc) of each first surface S1 and each second surface S2 of the electrolytic copper foil 110 ranges from 5 to 110, and the plating amount (DA) of chromium (Cr) of each first surface S1 and each second surface S2Cr) Ranging from 0.5mg/m2To 3.8mg/m2And the maximum surface roughness (R) of each of the first surfaces S1 and each of the second surfaces S2max) Ranging from 0.4 μm to 3.5 μm.
Meanwhile, a difference between the peak count (Pc) of the first surface S1 and the peak count (Pc) of the second surface S2 is less than or equal to 60. When the difference between the peak count (Pc) of the first surface S1 and the peak count (Pc) of the second surface S2 exceeds 60, there is a risk of a decrease in the capacity retention rate of the secondary battery due to the difference in the surface structures of the first surface S1 and the second surface S2.
Hereinafter, a method of manufacturing the electrolytic copper foil 110 will be described in detail according to an embodiment of the present invention.
First, the copper layer 111 is formed by supplying electricity between positive and negative electrode rotating drums spaced apart from each other, which are disposed in an electrolyte containing 70 to 90g/L of copper ions and 50 to 150g/L of sulfuric acid. According to an embodiment of the invention, the passing current density is 40A/dm2To 80A/dm2The current of (3) was applied to form a copper layer 111 on the negative electrode rotating drum.
According to the present invention, when the copper layer 111 is formed, the electrolyte is maintained so that the total carbon amount (TC) in the electrolyte is maintained at 0.25g/L or less. The total carbon amount (TC) may include a total organic carbon amount (TOC) and a total inorganic carbon amount (TIC), and may be analyzed by a TC measurement device.
In order to maintain the TC of the electrolyte at 0.25g/L or less, a high-purity copper wire is heat-treated to sinter organic substances, the heat-treated copper wire is pickled, and an electrolyte with little or no impurities is prepared by putting the pickled copper wire into sulfuric acid. The temperature range of the heat treatment of the copper wire may be 600 to 900 ℃, and the time of the heat treatment may be 30 to 60 minutes.
Meanwhile, the method of the present invention may further comprise: while the plating was performed, 31m3Hour to 45m3Continuous filtration (continuous filtration) is carried out at a flow rate of/hour to remove solid impurities from the electrolyte. When the flow rate is less than 31m3In/hour, the flow rate is decreased and the voltage is increased, and the copper layer 111 will be formed unevenly. On the other hand, when the flow rate is more than 45m3In/hour, the filter is damaged and foreign materials from the outside may be introduced into the electrolyte.
Optionally, the total carbon content (TC) may be reduced by decomposing organic matter in the electrolyte by ozone treatment.
Optionally, the cleanliness of the electrolyte may be improved by adding hydrogen peroxide and air to the electrolyte as the plating is being performed.
According to an embodiment of the present invention, when the copper layer 111 is formed (i.e., when electroplating is performed), the concentration of silver (Ag) in the electrolyte is maintained at 0.2g/L or less. The electrolyte may further include a small amount of chloride ions that can react with silver (Ag) to form silver chloride (AgCl) precipitates, so as to prevent the concentration of silver (Ag) in the electrolyte from exceeding 0.2g/L due to the addition of silver when performing electroplating. For example, the electrolyte may contain 50ppm or less of chloride ions (Cl)-)。
By controlling the silver (Ag) concentration and the total carbon amount (TC) within the above-mentioned ranges, and providing 40A/dm2To 80A/dm2Current density of (d), peak count (Pc) and maximum surface roughness (R) of the first surface S1 of the electrolytic copper foil 110max) Can be controlled in the ranges of 5 to 110 and 0.4 to 3.5 μm, respectively.
Optionally, the electrolyte may further include an organic additive selected from the group consisting of hydroxyethyl cellulose (HEC), an organic sulfide, an organic nitride, and a thiourea compound.
Then, the first protective layer 112a and the second protective layer 112b are formed on the copper layer 111 by soaking the copper layer 111 manufactured as described above in an antirust solution containing 0.5g/L to 1.5g/L of chromium (for example, soaking at room temperature for 2 seconds to 20 seconds) and drying the copper layer 111.
When the concentration of chromium (Cr) in the rust preventive solution is less than 0.5g/L, the plating amount (DA) of chromium on the surface of the electrolytic copper foil 110Cr) Less than 0.5mg/m2Resulting in oxidation of the surface of the electrolytic copper foil 110 and reduction of chemical bonding force between the electrolytic copper foil 110 and the first and second active material layers 120a and 120b, respectively.
On the other hand, when the concentration of chromium (Cr) in the rust preventive solution is more than 1.5g/L, the plating amount of chromium (DA) on the surface of the electrolytic copper foil 110Cr) More than 3.8mg/m2The hydrophobicity of the surface of the electrolytic copper foil 110 is significantly increased and the chemical affinity of the negative active material is lowered, eventually resulting in a decrease in the adhesion between the electrolytic copper foil 110 and the first and second active material layers 120a and 120b, respectively.
The rust inhibitive solution may further include at least one of a silane compound and a nitrogen compound. For example, the rust inhibitive solution may include 0.5g/L to 1.5g/L of chromium (Cr) and 0.5g/L to 1.5g/L of a silane compound.
Meanwhile, when the concentration of copper (Cu) in the rust preventive solution is too high, the plating amount of chromium (DA) on the surface of the copper layer 111Cr) And (4) reducing. Therefore, according to the embodiment of the present invention, the copper (Cu) concentration in the rust inhibitive solution is maintained at 0.1g/L or less. When the concentration of copper (Cu) is more than 0.1g/L, the plating amount of chromium (DA) on the surface of the electrolytic copper foil 110Cr) Less than 0.5mg/m2This results in oxidation of the surface of the electrolytic copper foil 110 and reduction of chemical bonding force between the electrolytic copper foil 110 and the first and second active material layers 120a and 120b, respectively.
Meanwhile, by adjusting the degree of polishing of the surface of the negative electrode rotating drum, for example, the surface on which the plating is performed to deposit copper, the peak count (Pc) and the maximum surface roughness (R) of the second surface S2 of the electrolytic copper foil 110max) Can be controlled to be 5 μm to 110 μm and 0.4 μm to 3.5 μm, respectively.
According to the embodiment of the present invention, the surface of the negative electrode rotating drum is ground using a grinding brush having a particle diameter (Grit) of #800 to # 1500.
The battery electrode (e.g., anode) of the present invention may be manufactured by coating the negative active material on the electrolytic copper foil 110 manufactured as described above.
The negative active material may be selected from the group consisting of carbon, a metal, an alloy including the foregoing metal, an oxide of the foregoing metal, and a composite of the foregoing metal and carbon, wherein the foregoing metal is, for example, silicon, germanium, tin, lithium, zinc, magnesium, cadmium, cerium, nickel, or iron.
For example, 1 to 3 parts by weight of Styrene Butadiene Rubber (SBR) and 1 to 3 parts by weight of carboxymethyl cellulose (CMC) are mixed in 100 parts by weight of carbon of the anode active material, and then a slurry is prepared using distilled water as a solvent. Then, a paste having a thickness of 20 to 100 μm is coated on the electrolytic copper foil 110 by using a doctor blade and is applied at a temperature of 110 to 130 ℃ at 0.5 ton/cm2To 1.5 tons/cm2Is pressurized.
Lithium batteries can be manufactured together using conventional cathodes, electrolytes and separators, and battery electrodes (or anodes) manufactured as described above.
The present invention will be described in detail below with reference to examples and comparative examples. However, the following examples are only examples to help understanding of the present invention, and the scope of the present invention is not limited to these examples.
Examples 1 to 4 and comparative examples 1 to 25
The copper layer is formed by supplying electricity between a positive electrode plate and a negative electrode rotating drum spaced apart from each other. The positive and negative rotating drums were placed in an electrolyte containing 75g/L of copper ions, 100g/L of sulfuric acid, and 0.08g/L of silver (Ag), and maintained at a temperature of 55 ℃. While the plating was performed, 37m3The flow rate per hour was continuously filtered to remove solid impurities from the electrolyte.
The copper layer is immersed in an antirust solution and then dried to prepare an electrolytic copper foil.
Here, the total carbon amount (TC) in the electrolytic solution, the applied current density for plating, the chromium (Cr) concentration in the rust preventive solution, and the copper (Cu) concentration in the rust preventive solution are shown in table 1 below.
[ Table 1]
Figure BDA0001386668830000121
Figure BDA0001386668830000131
The peak count (Pc) of the electrolytic copper foils, the plating amounts (DA) of chromium in the electrolytic copper foils of examples 1 to 4 and comparative examples 1 to 25 manufactured as described above were measured or calculated as followsCr) Maximum surface roughness (R)max) The adhesion coefficient (ADF), and the adhesion to the active material layer of each first surface (e.g., the surface of the electrolytic copper foil facing the matte side of the copper layer), the results of which are shown in table 2 below.
Peak count (Pc) (ea)
The peak count of each point of the first surface of the electrolytic copper foil was measured using a Mahrsurf M300 illuminometer manufactured by Mahr.
As described above, in the surface roughness profile obtained according to U.S. standard ASME B46.1-2009, the peak count (Pc) is the average of the peak counts of any three points, and the peak count of each point is the number of effective peaks of the upper standard line rising more than 0.5 μm per unit sample length of 4 mm. When there are no peaks of the lower standard line below-0.5 μm between adjacent peaks rising above the upper standard line, the relatively lower peaks between the effective peaks are ignored in obtaining the number of "effective peaks".
Cr 2Plating amount of chromium (DA) (mg/m)
Plating amount of chromium (DA)Cr) The determination was made by analyzing the solution obtained from the first surface of the electrolytic copper foil dissolved in dilute nitric acid (30 wt%) using Atomic Absorption Spectroscopy (AAS).
maxMaximum surface roughness (R) (mum)
The maximum surface roughness (R) was measured by using a Mahrsurf M300 luminometer manufactured by Mahr in accordance with Japanese Industrial Standard (JIS) B0601-max) (measurement length: 4 mm).
Coefficient of Adhesion (ADF)
The peak count (Pc) provided by the first surface of the electrolytic copper foil obtained as described above, the plating amount (DA) of chromiumCr) Maximum surface roughness (R)max) The adhesion coefficient (ADF) is calculated by applying to the following equation 1.
Equation 1: ADF Pc/10+ DACr/(mg/m2)+Rmax/μm
Adhesion to active Material layer (N/m)
(a) Sample preparation
2 parts by weight of SBR (styrene-butadiene rubber) and 2 parts by weight of CMC (carboxymethyl cellulose) were mixed in 100 parts by weight of carbon commercially available as a negative electrode active material. Then, a slurry was prepared using distilled water as a solvent. The slurry prepared in this manner was applied on the surface of an electrolytic copper foil, and a slurry (negative electrode active material slurry) having a thickness of 80 μm was coated on the surface of the electrolytic copper foil by using a doctor blade. Then, drying was performed at a temperature of 120 ℃, followed by preparing an anode by subjecting it to a roll press method. A sample of 10mm (width) × 100mm (length) was obtained by cutting the electrode prepared in this manner.
(b) Adhesion measurement
The active material portion of the sample was adhered to a reinforcing plate using a double-sided tape (3M VHB type), and then the peel strength between the electrolytic copper foil and the active material was measured according to the hydrochloric acid test method using an ultrasonic thickness meter (tensile speed: 50.0 mm/min, measurement length: 10mm, 90 ° peel test). The peel strength measured in this manner is the adhesion of the sample.
[ Table 2]
Figure BDA0001386668830000151
Figure BDA0001386668830000161
According to the present invention, a long-life secondary battery capable of maintaining a high charge and discharge capacity for a long time despite repeated charge and discharge cycles can be manufactured. Accordingly, consumer inconvenience and resource waste of electronic products due to frequent replacement of the storage battery can be minimized.

Claims (17)

1. An electrolytic copper foil for a battery, the electrolytic copper foil comprising a first surface and a second surface opposite the first surface, the electrolytic copper foil comprising:
a copper layer comprising a matte side facing the first surface and a glossy side facing the second surface; and
a first protective layer disposed on the matte side of the copper layer, the first protective layer comprising chromium (Cr);
wherein the adhesion coefficient of the surface defined by the following equation 1 ranges from 1.5 to 16.3:
equation 1: ADF Pc/10+ DACr+Rmax；
Where ADF denotes the adhesion coefficient, Pc denotes the peak count, DACrRepresents the plating amount of chromium (Cr) in mg/m2，RmaxRepresents the maximum surface roughness in μm;
wherein the peak count of the first surface ranges from 5 to 110, and the plating amount of chromium (Cr) of the first surface ranges from 0.5mg/m2To 3.8mg/m2And the maximum surface roughness of the first surface ranges from 0.4 μm to 3.5 μm,
where Pc represents the number of effective peaks in the surface roughness profile that rise above the upper standard line.
2. The electrolytic copper foil according to claim 1, further comprising a second protective layer disposed on the glossy surface of the copper layer, wherein the second protective layer comprises chromium (Cr), and an adhesion coefficient of the second surface is 1.5 to 16.3.
3. The electrolytic copper foil of claim 2, wherein a peak count (Pc) of the second surface ranges from 5 to 110, and a plating amount of chromium (Cr) of the second surface ranges from 0.5mg/m2To 3.8mg/m2And the maximum surface roughness of the second surface ranges from 0.4 μm to 3.5 μm.
4. The electrolytic copper foil according to claim 3, wherein the electrolytic copper foil has a yield strength of 21kgf/mm at room temperature2To 63kgf/mm2。
5. The electrolytic copper foil according to claim 1, wherein the electrolytic copper foil has an elongation of 3% or more at room temperature.
6. A battery electrode, comprising:
an electrolytic copper foil including a first surface and a second surface opposite to the first surface; and
a first active material layer disposed on the first surface of the electrolytic copper foil;
wherein the electrolytic copper foil comprises:
a copper layer comprising a matte side facing the first surface and a glossy side facing the second surface; and
a first protective layer disposed on the matte side of the copper layer, the first protective layer comprising chromium (Cr);
wherein an adhesion coefficient of the first surface of the electrolytic copper foil defined by the following equation 1 ranges from 1.5 to 16.3:
equation 1: ADF Pc/10+ DACr+Rmax；
Where ADF denotes the adhesion coefficient, Pc denotes the peak count, DACrRepresents the plating amount of chromium (Cr) in mg/m2，RmaxThe maximum surface roughness is expressed in terms of,the unit is the unit of μm,
where Pc represents the number of effective peaks in the surface roughness profile that rise above the upper standard line.
7. The battery electrode according to claim 6, wherein the first active material layer includes at least one active material selected from the group consisting of carbon, a metal, an alloy including the metal, an oxide of the metal, and a composite of the metal and carbon, the metal being silicon, germanium, tin, lithium, zinc, magnesium, cadmium, cerium, nickel, or iron.
8. The battery electrode of claim 6, wherein the first active material layer comprises silicon.
9. The battery electrode according to claim 6, wherein the electrolytic copper foil further comprises a second protective layer disposed on the glossy surface of the copper layer, and the battery electrode further comprises a second active material layer disposed on the second protective layer.
10. The battery electrode according to claim 6, wherein the adhesion between the electrolytic copper foil and the first active material layer is greater than or equal to 25N/m.
11. A battery, comprising:
a cathode;
an anode comprising a battery electrode according to any one of claims 6 to 10;
an electrolyte configured to provide an environment in which lithium ions can move between the cathode and the anode; and
a separator configured to electrically insulate the anode from the cathode.
12. A method of manufacturing an electrolytic copper foil for a secondary battery, the method comprising:
forming a copper layer by supplying electricity between a positive electrode plate and a negative electrode rotating drum spaced apart from each other, wherein the positive electrode plate and the negative electrode rotating drum are disposed in an electrolyte containing 70g/L to 90g/L of copper ions and 50g/L to 150g/L of sulfuric acid; and
forming a protective layer on the copper layer,
wherein the step of forming the copper layer comprises:
carrying out heat treatment on the copper wire;
pickling the overheated copper wire;
preparing the electrolyte by putting the acid-washed copper wire into sulfuric acid;
by providing a current density of 40A/dm between said positive and said negative rotating drum2To 80A/dm2Electroplating is carried out by the current; and
when the plating is performed, the thickness is 31m3Hour to 45m3Continuous filtration is carried out at a flow rate per hour to remove solid impurities from the electrolyte,
wherein, at the time of electroplating, the total carbon amount (TC) in the electrolyte is maintained at 0.25g/L or less, the silver (Ag) concentration in the electrolyte is maintained at 0.2g/L or less, and
the formation of the protective layer includes immersing the copper layer in an antirust solution containing 0.5 to 1.5g/L of chromium.
13. The method for manufacturing electrolytic copper foil for secondary batteries according to claim 12, wherein the copper wire is heat-treated at a temperature ranging from 600 ℃ to 900 ℃ for a time ranging from 30 minutes to 60 minutes.
14. The method of manufacturing electrolytic copper foil for secondary batteries according to claim 12, wherein the electrolyte further comprises chloride ions capable of reacting with silver (Ag) to silver chloride (AgCl) precipitates to avoid silver (Ag) concentration in the electrolyte exceeding 0.2g/L due to the addition of silver at the time of electroplating.
15. The method for manufacturing electrolytic copper foil for secondary batteries according to claim 12, wherein the forming of the copper layer further comprises: hydrogen peroxide and air are added to the electrolyte while electroplating is being performed.
16. The method for manufacturing an electrolytic copper foil for a storage battery according to claim 12, wherein a copper (Cu) concentration in the rust-preventive solution is maintained at 0.1g/L or less.
17. The method for manufacturing electrolytic copper foil for secondary batteries according to claim 12, wherein the electrolytic solution further comprises an organic additive selected from the group consisting of hydroxyethyl cellulose, organic sulfides, organic nitrides and thiourea-based compounds.
CN201710729000.9A 2016-08-23 2017-08-23 Electrolytic copper foil, electrode, secondary battery, and method for producing electrolytic copper foil Active CN107768674B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2016-0107230 2016-08-23
KR1020160107230A KR102669501B1 (en) 2016-08-23 Electrolytic Copper Foil, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same

Publications (2)

Publication Number Publication Date
CN107768674A CN107768674A (en) 2018-03-06
CN107768674B true CN107768674B (en) 2020-12-08

Family

ID=59686865

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710729000.9A Active CN107768674B (en) 2016-08-23 2017-08-23 Electrolytic copper foil, electrode, secondary battery, and method for producing electrolytic copper foil

Country Status (5)

Country Link
US (1) US10644320B2 (en)
EP (1) EP3288102A1 (en)
JP (1) JP6505169B2 (en)
CN (1) CN107768674B (en)
TW (1) TWI659557B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102439621B1 (en) * 2017-09-01 2022-09-01 에스케이넥실리스 주식회사 Copper Film, Manufacturing Methods Thereof, And Anode For Li Secondary Battery Comprising The Same
KR102103765B1 (en) * 2018-05-16 2020-04-28 일진머티리얼즈 주식회사 Electrolytic Copper Foil and secondary battery using thereof
JP7335886B2 (en) * 2018-09-28 2023-08-30 古河電気工業株式会社 Insulation coating compound superconducting wire and its rewinding method
TWI700393B (en) * 2019-08-27 2020-08-01 長春石油化學股份有限公司 Electrolytic copper foil and electrode and lithium ion cell comprising the same
CN113663596B (en) * 2021-09-02 2022-10-28 灵宝宝鑫电子科技有限公司 Static pool additive dynamic adding system

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101146933A (en) * 2005-03-31 2008-03-19 三井金属矿业株式会社 Electrolytic copper foil and process for producing electrolytic copper foil, surface treated electrolytic copper foil using said electrolytic copper foil, and copper-clad laminate plate and printed wi
KR20110135219A (en) * 2010-06-10 2011-12-16 일진머티리얼즈 주식회사 Electrolyte for manufacturing electrolytic copper foil of secondary battery and method for manufacturing electrolytic copper foil therewith
CN103314474A (en) * 2010-12-27 2013-09-18 古河电气工业株式会社 Lithium-ion secondary battery, electrode for secondary battery, and electrolytic copper foil for secondary battery electrode
CN103911633A (en) * 2013-01-07 2014-07-09 长春石油化学股份有限公司 Electrolytic copper foil and method for producing the same
CN104805478A (en) * 2014-01-29 2015-07-29 金居开发铜箔股份有限公司 Electrolytic copper foil for negative current collector and manufacturing method thereof

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07107181B2 (en) 1987-08-27 1995-11-15 日鉱金属株式会社 Copper material for superconductivity
US6132887A (en) 1995-06-16 2000-10-17 Gould Electronics Inc. High fatigue ductility electrodeposited copper foil
JP3850155B2 (en) * 1998-12-11 2006-11-29 日本電解株式会社 Electrolytic copper foil, copper foil for current collector of secondary battery and secondary battery
US6372113B2 (en) * 1999-09-13 2002-04-16 Yates Foil Usa, Inc. Copper foil and copper clad laminates for fabrication of multi-layer printed circuit boards and process for producing same
JP3794613B2 (en) 2000-05-18 2006-07-05 三井金属鉱業株式会社 Electrolytic equipment for electrolytic copper foil
KR100389061B1 (en) 2002-11-14 2003-06-25 일진소재산업주식회사 Electrolytic copper foil and process producing the same
JPWO2004049476A1 (en) 2002-11-27 2006-03-30 三井金属鉱業株式会社 Negative electrode current collector for non-aqueous electrolyte secondary battery and method for producing the same
WO2008132987A1 (en) 2007-04-20 2008-11-06 Nippon Mining & Metals Co., Ltd. Electrolytic copper foil for lithium rechargeable battery and process for producing the copper foil
JP4948654B2 (en) 2010-03-01 2012-06-06 古河電気工業株式会社 Copper foil for negative electrode current collector of lithium ion secondary battery, manufacturing method thereof, negative electrode of lithium ion secondary battery, manufacturing method thereof
US20140127569A1 (en) 2011-04-12 2014-05-08 Mitsui Mining & Smelting Co., Ltd. Copper foil provided with chromate film for negative electrode current collector, and negative electrode material using the copper foil provided with chromate film for negative electrode current collector
WO2013129588A1 (en) 2012-02-28 2013-09-06 古河電気工業株式会社 Lithium ion secondary battery, collector constituting negative electrode of lithium ion secondary battery, and electrolytic copper foil constituting negative electrode collector
JP5954624B2 (en) 2012-06-05 2016-07-20 グンゼ株式会社 Degreasing apparatus and degreasing method
JP5718476B2 (en) 2012-06-27 2015-05-13 古河電気工業株式会社 Electrolytic copper foil for lithium ion secondary battery, negative electrode of lithium ion secondary battery, and lithium ion secondary battery
CN104321469A (en) 2012-12-27 2015-01-28 古河电气工业株式会社 Low spring-back electrolytic copper foil, and circuit board and flexible circuit board using said electrolytic copper foil
PL3316363T3 (en) 2015-06-24 2022-08-01 Sk Nexilis Co., Ltd. Electrolytic copper foil, current collector including same electrolytic copper foil, electrode including same current collector, secondary battery including same electrode, and method for manufacturing same
CN105002550A (en) * 2015-07-14 2015-10-28 灵宝华鑫铜箔有限责任公司 Device and process for reducing concentration of lead ions in electrolyte of electrolytic copper foil

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101146933A (en) * 2005-03-31 2008-03-19 三井金属矿业株式会社 Electrolytic copper foil and process for producing electrolytic copper foil, surface treated electrolytic copper foil using said electrolytic copper foil, and copper-clad laminate plate and printed wi
KR20110135219A (en) * 2010-06-10 2011-12-16 일진머티리얼즈 주식회사 Electrolyte for manufacturing electrolytic copper foil of secondary battery and method for manufacturing electrolytic copper foil therewith
CN103314474A (en) * 2010-12-27 2013-09-18 古河电气工业株式会社 Lithium-ion secondary battery, electrode for secondary battery, and electrolytic copper foil for secondary battery electrode
CN103911633A (en) * 2013-01-07 2014-07-09 长春石油化学股份有限公司 Electrolytic copper foil and method for producing the same
CN104805478A (en) * 2014-01-29 2015-07-29 金居开发铜箔股份有限公司 Electrolytic copper foil for negative current collector and manufacturing method thereof

Also Published As

Publication number Publication date
TW201807869A (en) 2018-03-01
US20180062180A1 (en) 2018-03-01
JP2018031072A (en) 2018-03-01
KR20180022208A (en) 2018-03-06
JP6505169B2 (en) 2019-04-24
CN107768674A (en) 2018-03-06
US10644320B2 (en) 2020-05-05
EP3288102A1 (en) 2018-02-28
TWI659557B (en) 2019-05-11

Similar Documents

Publication Publication Date Title
CN107768674B (en) Electrolytic copper foil, electrode, secondary battery, and method for producing electrolytic copper foil
JP6619457B2 (en) Electrolytic copper foil, current collector including the same, electrode including the same, secondary battery including the same, and manufacturing method thereof
EP3288101B1 (en) Electrolytic copper foil capable of improving capacity retention rate of secondary battery, electrode including the same, secondary battery including the same, and method of manufacturing the same
CN107946596B (en) Easy-to-handle electrolytic copper foil, electrode and secondary battery including the same, and method of manufacturing the same
CN108270015B (en) Electrolytic copper foil, electrode, secondary battery, and method for producing same
CN108270016B (en) Electrolytic copper foil, electrode, secondary battery and method for manufacturing same
CN108475790B (en) Copper foil, method for manufacturing the same, electrode including the copper foil, and secondary battery including the electrode
CN108574104B (en) Copper foil, electrode comprising the same, secondary battery comprising the same, and method for manufacturing the same
KR20180090532A (en) High Strength Electrolytic Copper Foil with Minimized Wrinkle and Curl, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same
KR102669501B1 (en) Electrolytic Copper Foil, Electrode Comprising The Same, Secondary Battery Comprising The Same, and Method for Manufacturing The Same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20180827

Address after: Gyeonggi Do, South Korea

Applicant after: KCF Technology Co., Ltd.

Address before: South Korea Gyeonggi Do Anyang

Applicant before: Ls Megtron Co.

GR01 Patent grant
GR01 Patent grant
CP03 Change of name, title or address
CP03 Change of name, title or address

Address after: Han Guoquanluobeidao

Patentee after: Sk Nashi Co.,Ltd.

Address before: Han Guojingjidao

Patentee before: KCF Technology Co.,Ltd.